CN101679140A - Mto process based on meapo molecular sieves combined with an ocp process to make olefins - Google Patents

Abstract

The present invention relates to a process to make light olefins from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising: contacting said oxygen-containing,halogenide-containing or sulphur-containing organic feedstock in a primary reactor with a catalyst made of a metalloaluminophosphate (MeAPO) molecular sieve with lamellar crystal morphology at conditions effective to convert at least a portion of the feedstock to form a first reactor effluent comprising light olefins and a heavy hydrocarbon fraction; separating said light olefins from said heavyhydrocarbon fraction; contacting said heavy hydrocarbon fraction in a second reactor at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to light olefins; whereinsaid MeAPO has an empirical chemical composition on an anhydrous basis, after synthesis and calcination, expressed by the formula HxMeyAlzPkO2 in which, y+z+k=1 x<=y, y has a value ranging from 0.0008to 0.4 and advantageously from 0.005 to 0.18, z has a value ranging from 0.25 to 0.67 and advantageously from 0.38 to 0.55, k has a value ranging from 0.2 to 0.67 and advantageously from 0.36 to 0.54said molecular sieve having predominantly a plate crystal morphology in which the width (W) and the thickness (T) are such as: W/T is >= 10 and advantageously ranges from 10 to 100.

Description

Based on the methanol conversion of metal tripolyphosphate aluminum molecular screen is that olefin process and cracking of olefins process combination are to make alkene

Technical field

The present invention relates to MTO (methanol conversion is an alkene) technology based on the MeAPO molecular sieve and OCP (cracking of olefins technology) process combination to make alkene.Or rather, MTO technology is based on metal tripolyphosphate aluminium (MeAPO) molecular sieve catalyst with layered crystal form.The limited supply of crude oil and the cost that improves constantly have promoted the research to the alternative method that is used to make hydrocarbon product.A kind of such method is to be hydrocarbon with methanol conversion and especially to be converted into light olefin.To methanol conversion is that the concern of alkene (MTO) technology is based on the following fact: methyl alcohol can be by coal or Sweet natural gas by making synthetic gas, synthetic gas processed to make methyl alcohol to obtain then.MTO technology produces for example for example butylene and above hydrocarbon of ethene and propylene and heavy hydrocarbon of light olefin.With the cracking in OCP technology of these heavy hydrocarbons, mainly obtain ethene and propylene.

Background technology

In US 2,006 0235251, WO 2,005 016856, US 2,006 0063956, US 20060161035, US 6207872, US 2,005 0096214, US 6953767 and US 7067095, MTO technology has been described.

Ethene and propylene are special ideal alkene, but have found their yield in MTO technology because the hydrocarbon of medium wt C for example ₄, C ₅And C ₆The generation of alkene and some heavy components and reducing.The products distribution of MTO technology that needs method to change to be used for to make light olefin is to provide technological flexibility.Seek the C that makes from MTO technology ₄, C ₅More the output of higher alkene is with respect to the method for ethene and propone output minimizing.Therefore, with OCP technology and MTO process combination so that from the C of MTO technology ₄, C ₅More higher alkene cracking.It is the economy of olefin process that this yield improvement of ethene and propylene has significantly improved methanol conversion.

WO1999 018055 relates to the method that the light olefin yield of oxygenatedchemicals during the conversion of olefines improved, and comprising: oxygen-containing compound material is contacted effectively producing under the first condition that comprises light olefin and first product of heavy hydrocarbon fraction (fraction) with the non-zeolitic molecular sieves catalyzer in first reactor (MTO reactor); Described light olefin is separated with described heavy hydrocarbon fraction; In described heavy hydrocarbon fraction charging second reactor; With make described heavy hydrocarbon fraction experience in described second reactor at least a portion of described heavy hydrocarbon effectively is converted into the second condition of light olefin.The suitable SAPO that is used for the MTO reactor comprises SAPO-11, SAPO-44, SAPO-34, SAPO-17 and SAPO-18.The preferred zeolite that is used for auxiliary reactor is ZSM-5.

US 20040102667 relates to by the method that contains oxygen feed stream manufacturing light olefin.This invention relate more specifically to by make methanol conversion be produce in the olefin process improve the method for light olefin yield than the heavy olefins cracking.

Have been found that in the MTO OCP technology of combination, in the MTO reactor, use special catalyst to cause very high propylene yield.Described special catalyst is made by metal tripolyphosphate aluminium (MeAPO) molecular sieve with layered crystal form, and this metal tripolyphosphate aluminium (MeAPO) molecular sieve has by formula H after synthetic and calcining _xMe _yAl _zP _kO ₂The experience chemical constitution on anhydrous basis of expression, wherein

y+z+k＝1

x≤y

Y has 0.0008～0.4 and advantageously 0.005～0.18 value,

Z has 0.25～0.67 and advantageously 0.38～0.55 value,

K has 0.2～0.67 and advantageously 0.36～0.54 value,

Described molecular sieve mainly has the platelet form, and wherein width (W) and thickness (T) satisfy:

W/T 〉=10 advantageously are 10～100 also.

In preferred embodiment, T≤0.15 μ m, that better is T≤0.10 μ m, and that better is T≤0.08 μ m, and T advantageously is 0.01～0.07 μ m and is preferably 0.04～0.07 μ m.

In the presence of a kind of template, a kind of structure influence agent (texture influencing agent), inorganic metal source, Al source and the P source and all these compositions be the described MeAPO of preparation under the specific ratio situation, obtain MeAPO with extremely thin stratified pieces crystalline form attitude.Described template can be tetraethyl ammonium hydroxide (TEAOH) or amine.Described structure influence agent can be alcohol, glycol or glycerine.

Following description of the Prior Art MeAPO, but they are not the thin layer shapes.All these prior aries relate to the MeAPO with stratiform cubic system or platelet form.In all these prior aries, only used a kind of template.And, the combination of MTO-OCP is not described.

US 4,440, and 871 have described microporous crystalline silicon aluminium phosphate (being called SAPO), and its hole is uniformly and has specific diameter greater than about 3 dusts, and its be synthesized out in the basic experience chemical constitution of (as-synthesized) and anhydrous form be mR; (Si _xAl _yP _z) O ₂, wherein " R " expression is present at least a organic formwork agent in the intracrystalline pore system; " m " has 0.02～0.3 value; " m " expression is with respect to every mole of (Si _xAl _yP _z) O ₂The mole number of " R " that exists; " x ", " y " and " z " represent that respectively described molar fraction makes them at ternary phase diagrams (ternary diagram) Si as the molar fraction of silicon, aluminium and the phosphorus of tetrahedral oxide existence _xAl _yP _zThe specific region in.The method that is used to prepare described SAPO comprises: form and contain reactive SiO ₂Source, reactive Al ₂O ₃Source, reactive P ₂O ₅The reaction mixture of source and organic formwork agent, described reaction mixture has the composition of representing with oxide mol ratio: aR ₂O: (Si _xAl _yP _z) O ₂: bH ₂O, wherein " R " is organic formwork agent, and " a " has even as big as the value of " R " that constitutes significant quantity and its in greater than 0 to 3 scope, and " b " has 0～500 value, and " x ", " y " and " z " represent (Si respectively _xAl _yP _z) O ₂The molar fraction of silicon, aluminium and phosphorus also has at least 0.01 value separately in the component; With make thus the reaction mixture that forms under at least 100 ℃ temperature crystallization until the crystal that forms silicon aluminium phosphate.

US 6,207, and 872 to relate to methanol conversion be the method for light olefin, comprise methyl alcohol is contacted under conversion condition with catalyzer that described catalyzer comprises crystalline state metal tripolyphosphate aluminum molecular screen, and this crystalline state metal tripolyphosphate aluminum molecular screen has by empirical formula (EL _xAl _yP _z) O ₂The chemical constitution on anhydrous basis of expression, wherein EL is the metal that is selected from silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and composition thereof, " x " is the molar fraction of EL and has at least 0.005 value, " y " is the molar fraction of Al and has at least 0.01 value, " z " is the molar fraction of P and has at least 0.01 value and x+y+z=1, described molecular sieve is characterised in that it mainly has the platelet form, and wherein average minimum crystal dimension is at least 0.1 micron and have and be less than or equal to 5 aspect ratio.

US 6,334, and 994 relate to the crystallne phosphoric acid silicon aluminium composition of micropore, and it consists of in synthetic and the theory of calcining back on anhydrous basis: H _wSi _xAl _yP _zO ₂Wherein w and x have 0.01～0.05 value, and y and z are 0.4～0.6 value, wherein said composition is to be included in the silicon aluminium phosphate of the AEI of preparation in one batch the crystallisation process (onebatch crystallization) and CHA structure and the mixed phase product that do not comprise pure physical mixture, described product under 550 ℃ in air calcining produce specific x-ray diffraction pattern and XRD-profile after 4 hours.

EP 893159 relates to the method for catalyzer that preparation comprises silica modified crystallne phosphoric acid Si-Al molecular sieve, and it comprises: aluminium alkoxide is joined in the aqueous solution of under not being higher than 20 ℃ temperature refrigerative amine or organic ammonium salt; With posthydrolysis, until forming uniform moisture alumine hydroxide colloid or solution; In this colloid or solution, add silicon oxide or other Si source compound and phosphoric acid or other P source compound, also can add the source metal that is selected from Li, Ti, Zr, V, Cr, Mn, Fe, Co, Zn, Be, Mg, Ca, B, Ga and Ge if desired; Hydrothermal treatment consists gained mixture is with preparation crystallne phosphoric acid Si-Al molecular sieve; With silicon oxide described crystallne phosphoric acid Si-Al molecular sieve is carried out modification then.

US 20050096214 (US 6953767) relates to by the method that contains oxygen feedstock production olefin product, be included under the condition of effective formation olefin product the described oxygen raw material that contains is contacted with the catalyzer that comprises silicoaluminophosphamolecular molecular sieves, described silicoaluminophosphamolecular molecular sieves comprises the coexisting phase of the molecular sieve of at least a AEI of having and CHA framework types, and wherein said coexisting phase has the powder x-ray diffraction pattern of the calcining sample that uses described silicoaluminophosphamolecular molecular sieves, analyzes about 5/95～40/60 the AEI/CHA ratio of determining by DIFFaX.

US 20050096214 (US 6953767) has also described the method for the molecular sieve for preparing described method, comprising:

(a) in the presence of organic structure directed agents (template), reactive silicon source, reactive phosphorus source and hydrated aluminum oxide are made up to form mixture;

(b) mixture for preparing in the step a) is mixed and heat until Tc continuously;

(c) with described mixture in the time of keeping 2～150 hours under the Tc and under stirring;

(d) crystal of recovery silicoaluminophosphamolecular molecular sieves;

(e) mole that has in following scope of the mixture that wherein prepares in the step a) is formed:

P ₂O ₅: Al ₂O ₃It is 0.6: 1～1.2: 1

SiO ₂: Al ₂O ₃It is 0.005: 1～0.35: 1

H ₂O: Al ₂O ₃It is 10: 1～40: 1

And described template is the tetraethyl ammonium compound.

In all these above-mentioned prior aries, only used template and/or special reaction condition to influence the crystalline structure of material.In US 6,540,970 subsequently, used the solvent in template and metal (Me) source.In an embodiment, the organosilicon source is positive tetraethyl orthosilicate.US 6,540, and 970 relate to the method for making metal tripolyphosphate aluminium (MeAPO) molecular sieve, and described method comprises the steps:

Alumina source, phosphorus source, water are provided and are suitable for forming the template of MeAPO molecular sieve;

Source metal is provided, and described source metal comprises metallic particles, and the overall dimension of described metallic particles is equal to or less than 5 nanometers;

The water-miscible organic solvent that can make described source metal solubilization is provided;

Form synthetic mixture by described alumina source, described phosphorus source, described water, described template, described source metal and described solvent;

With form the MeAPO molecular sieve by described synthetic mixture.

It is desirable to, can make the water-miscible organic solvent of described source metal solubilization be selected from sulfoxide and C ₁～C ₅Oxygen-containing hydrocarbon.It is desirable to, described oxygen-containing hydrocarbon is selected from alcohol (structure branching or positive), ketone, aldehyde, two pure and mild acid.The available solvent comprises and is selected from acetone, 1,2-propylene glycol, 1, one or more solvents in ammediol, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols and the ethylene glycol.It is desirable to, described solvent is an alcohol.Products therefrom for constitute the SAPO molecular sieve etc. crystalline state (isocrystalline) spheroidal particle.Described particulate diameter is 0.5 micron～30 microns.

Summary of the invention

The present invention relates to make the method for light olefin, comprising by containing oxygen, halide or sulfur-bearing organic raw material:

Described oxygen, halide or the sulfur-bearing organic raw material of containing contacted first reactor effluent that comprises light olefin and heavy hydrocarbon fraction to form with the catalyzer that is made by metal tripolyphosphate aluminium (MeAPO) molecular sieve with layered crystal form under the condition of at least a portion that transforms described raw material effectively in first reactor;

Described light olefin is separated with described heavy hydrocarbon fraction;

Described heavy hydrocarbon fraction under being converted into the condition of light olefin, at least a portion that makes described heavy hydrocarbon fraction is effectively contacted in second reactor;

Wherein said MeAPO has by formula H after synthetic and calcining _xMe _yAl _zP _kO ₂The experience chemical constitution on anhydrous basis of expression, wherein

y+z+k＝1

x≤y

Y has 0.0008～0.4 and advantageously be 0.005～0.18 value,

Z has 0.25～0.67 and advantageously be 0.38～0.55 value,

K has 0.2～0.67 and advantageously be 0.36～0.54 value,

Described molecular sieve mainly has the platelet form, and wherein width (W) and thickness (T) satisfy:

W/T 〉=10 and advantageously be 10～100.

The invention still further relates to by containing oxygen, halide or sulfur-bearing organic raw material and make the method for light olefin, comprising:

Described oxygen, halide or the sulfur-bearing organic raw material of containing contacted first reactor effluent that comprises light olefin and heavy hydrocarbon fraction to form with the catalyzer that is made by metal tripolyphosphate aluminium (MeAPO) molecular sieve under the condition of at least a portion that transforms described raw material effectively in first reactor;

Described light olefin is separated with described heavy hydrocarbon fraction;

Described heavy hydrocarbon fraction under being converted into the condition of light olefin, at least a portion that makes described heavy hydrocarbon fraction is effectively contacted in second reactor;

Wherein said MeAPO is prepared by a method comprising the following steps:

A) formation contains structure influence agent (TIA), organic formwork agent (TEMP), at least a reactive inorganic MeO that is insoluble to TIA basically ₂Source, reactive Al ₂O ₃Source and reactive P ₂O ₅The reaction mixture in source,

B) make the above reaction mixture crystallization of formation thus until the crystal that forms metal tripolyphosphate aluminium;

C) reclaim solid reaction product;

D) it is washed with water with remove described TIA and

E) it is calcined to remove described organic formwork.

Embodiment

About the catalyzer of first reactor, T≤0.15 μ m in a preferred embodiment, T≤0.10 μ m more desirably, T≤0.08 μ m more desirably, T advantageously is 0.01～0.07 μ m and is preferably 0.04～0.07 μ m.

In favourable embodiment, y has 0.005～0.18 value, and z has 0.38～0.55 value and k and has 0.36～0.54 value.

In first preferred implementation, y has 0.005～0.16 value, and z has 0.39～0.55 value and k and has 0.37～0.54 value.

In second preferred implementation, y has 0.011～0.16 value, and z has 0.39～0.55 value, and k has 0.37～0.54 value.

In the 3rd preferred implementation, y has 0.011～0.14 value, and z has 0.40～0.55 value, and k has 0.38～0.54 value.

In favourable embodiment, described MeAPO molecular sieve has structure C HA or AEI or its mixture on substantially.Preferably, they have structure SAPO 18 or SAPO 34 or its mixture basically.

About the platelet form, described advantageously has and comprises foursquare simple polygon shape.This foursquare length of side is W.Described MeAPO molecular sieve mainly has the platelet form.So-called " mainly " refers to advantageously the crystal greater than 50%.Preferred at least 70% crystal have lamellar morphology and most preferably at least 90% crystal have lamellar morphology.About relating to " basically " of CHA or AEI structure, it refers to advantageously greater than 80 weight %, the MeAPO of the present invention that is preferably greater than 90 weight % has structure C HA or AEI or its mixture.About relating to " basically " of SAPO 18 or SAPO 34 structures, it refers to advantageously greater than 80 weight %, the MeAPO that is preferably greater than 90 weight % has structure SAPO 18 or SAPO 34 or its mixture.

Me is advantageously for being selected from the metal of silicon, germanium, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and composition thereof.Preferred metal is silicon, magnesium and cobalt, and preferred especially silicon or germanium.

The MeAPO molecular sieve can directly be used as catalyzer.In another embodiment, can by with described molecular sieve with provide other combination of materials of extra hardness or catalytic activity that described molecular sieve is mixed with catalyzer for final catalyst product.Can be various inertia or catalytically active material with the material of described molecular sieve blend, perhaps various adhesive materials.These materials comprise for example following composition: various forms, aluminum oxide or alumina sol, titanium oxide, zirconium white, quartz, silicon oxide or the silica sol of kaolin and other clays, rare earth metal, and composition thereof.These components are effective for the intensity of the catalyzer that makes described catalyzer densification and raising preparation.When with non--during the blend of metal tripolyphosphate aluminum molecular screen material, the MeAPO amount that is contained in the final catalyst product is 10～90 weight % of total catalyst, is preferably 20～70 weight % of total catalyst.

About making the method for described MeAPO, it can be prepared by a method comprising the following steps:

A) influence agent (TIA), organic formwork agent (TEMP), at least a reactive inorganic MeO that is insoluble to TIA basically after formation contains ₂Source, reactive Al ₂O ₃Source and reactive P ₂O ₅The reaction mixture in source, described reaction mixture has the composition that shows with the oxide molar ratiometer:

TEMP/Al ₂O ₃=0.3～5, better is 0.5～2,

MeO ₂/ Al ₂O ₃=0.005～2.0, better is 0.022～0.8,

P ₂O ₅/ Al ₂O ₃=0.5～2, better is 0.8～1.2

TIA/Al ₂O ₃=3～30, better is 6～20;

B) make the above reaction mixture crystallization of formation thus until the crystal that forms metal tripolyphosphate aluminium;

C) reclaim solid reaction product;

D) it is washed with water with remove described TIA and

E) it is calcined to remove described organic formwork.

In favourable embodiment, TEMP/Al ₂O ₃=0.5～2; MeO ₂/ Al ₂O ₃=0.022～0.8; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

In first preferred implementation, TEMP/Al ₂O ₃=0.5～2; MeO ₂/ Al ₂O ₃=0.022～0.7; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

In second preferred implementation, TEMP/Al ₂O ₃=0.7～2; MeO ₂/ Al ₂O ₃=0.05～0.7; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

In the 3rd preferred implementation, TEMP/Al ₂O ₃=0.7～2; MeO ₂/ Al ₂O ₃=0.05～0.6; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

About TIA, can mention 1 as an example, 2-propylene glycol, 1, ammediol, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, glycerine or ethylene glycol.

About organic formwork agent, it can be and proposes to be used for synthetic those of conventional zeolite type pure aluminium silicate and microporous aluminophosphates arbitrarily so far.Usually these compounds contain the element of periodic table of elements VA family, particularly nitrogen, phosphorus, arsenic and antimony, and preferred N or P and N most preferably, and described compound also contains the alkyl or aryl that at least one has 1～8 carbon atom.Particularly preferred nitrogenous compound as template is amine and quaternary ammonium compound, and the latter uses formula R usually ₄N ⁺Expression, wherein each R is the alkyl or aryl that contains 1～8 carbon atom.Also suitably adopt for example [(C of polymer-type quaternary ammonium salt ₁₄H ₃₂N ₂) (OH) ₂] _X, wherein " x " has and is at least 2 value.Monoamine, diamine and tertiary amine all advantageously or separately use, and perhaps are used in combination with quaternary ammonium compound or other template compound.Representational template comprises: tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium or TBuA positively charged ion; Di-n-propyl amine, tripropylamine, triethylamine; Diethylamine, trolamine; Piperidines; Morpholine; Hexahydroaniline; The 2-picoline; N, the N-dimethyl benzylamine; N, the N-diethylethanolamine; Dicyclohexylamine; N, the N-dimethylethanolamine; Choline; N, N '-lupetazin; 1,4-diazabicylo (2,2,2) octane; N methyldiethanol amine, N-Mono Methyl Ethanol Amine, N-methyl piperidine; The 3-methyl piperidine; N-methylcyclohexylamine; The 3-picoline; The 4-picoline; Rubane; N, N '-dimethyl-1,4-diazabicylo (2,2,2) octane ion; Di-n-butyl amine, neo-pentyl amine; Two n-pentyl amine; Isopropylamine; Tert-butylamine; Quadrol; Tetramethyleneimine; With the 2-imidazolidone.Advantageously, organic formwork agent is selected from: tetraethyl ammonium hydroxide (TEAOH), diisopropyl ethyl amine (DPEA), tetraethyl-ammonium salt, cyclopentamine, aminomethyl hexanaphthene, piperidines, triethylamine, diethylamide, hexahydroaniline, triethyl ethylol amine, morpholine, dipropylamine, pyridine, isopropylamine, di-n-propyl amine, hydroxide tetra-n-butyl ammonium, diisopropylamine, di-n-propyl amine, normal-butyl ethylamine, di-n-butyl amine and two n-pentyl amine and combination thereof.Preferably, described template is for being selected from tetraethyl ammonium hydroxide (TEAOH), phosphoric acid tetraethyl ammonium, fluoridizing the tetraethyl ammonium compound in tetraethyl ammonium, tetraethylammonium bromide, etamon chloride, the acetate tetraethyl ammonium.Most preferably, described template is a tetraethyl ammonium hydroxide.

About being insoluble to TIA basically and relating to the reactive inorganic MeO of silicon ₂The source, the limiting examples that is insoluble to the available inorganic silicon source material of alcohol comprises fumed silica (fumed silica), aerosol, pyrogene silicon oxide (pyrogenic silica), precipitated silica and silica gel.

About reactive Al ₂O ₃The source, it can be any aluminum material that can be dispersed or dissolved in the moisture resulting solution.The available alumina source is to be selected from one or more following sources: hydrated aluminum oxide, organic oxidation aluminium is Al (OiPr) particularly ₃, class boehmite, aluminium hydroxide, colloidal alumina, aluminum halide, ALUMINUM CARBOXYLIC, Tai-Ace S 150, and composition thereof.

About reactive P ₂O ₅The source, it can be and is selected from one or more following sources: phosphoric acid; Organophosphate (salt), for example triethyl phosphate, phosphoric acid tetraethyl ammonium; Aluminum phosphate; And composition thereof.The phosphorus source also should be able to be dispersed or dissolved in the pure resulting solution.

These MeAPO can be by the ordinary method preparation of molecular sieve synthetic technology, as long as it is consistent with aforementioned proportion.Reaction mixture is a gel form.Ratio MeO ₂/ Al ₂O ₃And P ₂O ₅/ Al ₂O ₃In above-mentioned favourable and preferred ratio, select, and consistent with above-mentioned favourable and preferred y, z and k.For example, have y, z and k, must use according to the composition of second preferred implementation of described method than to make described MeAPO according to second preferred implementation in order to make MeAPO.

About step b), make by with reactive oxidants aluminium source, reactive MeO ₂Source, reactive phosphorus source, organic formwork agent and TIA mix and the reaction mixture experience autogenous pressure that obtains and the temperature of rising.Described reaction mixture is heated to can be about 120 ℃～250 ℃, be preferably 130 ℃～225 ℃, most preferably be 150 ℃～200 ℃ Tc.Be heated to Tc and carried out most preferably from about 2～9 hours usually about 0.5 hour～about 16 hours, preferred about 1～12 hour.Temperature can progressively or continuously improve.Yet, preferred heating continuously.During hydrothermal treatment consists, described reaction mixture can keep static or stir by upset or stirring reaction container.Preferably, with reaction mixture upset or stirring, most preferably stir.Then with temperature maintenance under Tc 2～200 hours.Heat and stirring apply one period that can form crystallized product effectively.In concrete embodiment, reaction mixture was kept under Tc 16～96 hours.

About step c), can use conventional mode.Usually, the crystalline state molecular sieve product forms slurry and can be by for example sedimentation of standard manner, centrifugal or filter and to reclaim.

About step d),,, and be dried by sedimentation, centrifugal or filter and reclaim with the washing of isolating molecular sieve product.

About step e), the calcining of molecular sieve itself is known.The result of crystallization of molecular sieves process is that the molecular sieve of recovery contains template used at least a portion in its hole.In preferred embodiment, activate in the mode that described template is removed from molecular sieve, thereby stay the active catalytic site and make the micro channel of described molecular sieve for for the contacting of raw material, being open.Described activating process usually by in the presence of oxygen-containing gas, 200～800 ℃ temperature lower calcination or necessarily the heating molecular sieve that comprises described template finish.In some cases, can be and it is desirable in having the environment of low oxygen concentration the described molecular sieve of heating.Such technology can be used for removing partially or completely template from intracrystalline pore system.

In addition, if between synthesis phase, used basic metal or alkaline-earth metal, then can make molecular sieve experience ion-exchange step.Usually, in the aqueous solution that uses ammonium salt or mineral acid, carry out ion-exchange.

About the MTO technology in first reactor, when oxygenatedchemicals is in gas phase, the described oxygen raw material that contains is contacted with catalyzer usually.Perhaps, can in liquid phase or gas/liquid mixed phase, implement this technology.In this oxygenate technology, can under wide temperature range, produce alkene usually.Effectively service temperature can be about 200 ℃～700 ℃.In the lower end of this temperature range, it is slow significantly that the formation of the olefin product of expectation can become.In the upper end of this temperature range, described method may not can form the product of optimum quantity.Preferably at least 300 ℃, and be up to 575 ℃ service temperature.

Pressure also can change in wide scope.Preferred pressure is about 5kPa～about 5MPa, and most preferred scope is about 50kPa～about 0.5MPa.Above-mentioned pressure is meant the dividing potential drop of oxygenatedchemicals and/or its mixture.

Described technology can be carried out in any system of using various conveying beds, although can use fixed bed or moving-bed system.Advantageously use fluidized-bed.It is desirable to this reaction process of operation under high space velocity especially.Described technology can be carried out in single conversion zone or be carried out in a plurality of conversion zones that serial or parallel connection is arranged.Can use any standard industry scale reaction body to be, for example fixed bed, fluidized-bed or moving-bed system.Plant-scale reactor system can be at 0.1h ^-1～1000h ^-1Down operation of weight hourly space velocity (WHSV).

Can have one or more inert diluents in the raw material, for example based on all raw materials that are fed to conversion zone and the total mole number of thinner composition, inert diluent exists with the amount of 1～95 mole of %.Typical thinner comprises, but be not necessarily limited to helium, argon gas, nitrogen, carbon monoxide, carbonic acid gas, hydrogen, water, paraffinic hydrocarbons (paraffin), alkane (particularly methane, ethane and propane), aromatic substance, and composition thereof.Preferable absorbent is water and nitrogen.Can with water can liquid or vapor form inject.

Containing the oxygen raw material is to contain to have at least one Sauerstoffatom and can be converted into the molecule of olefin product or any raw material of any chemical in the presence of above MeAPO catalyzer.Contain the oxygen raw material and comprise at least a organic compound that contains at least one Sauerstoffatom, for example fatty alcohol, ether, carbonyl compound (aldehyde, ketone, carboxylic acid, carbonic ether, ester etc.).Representational oxygenatedchemicals is including but not necessarily limited to rudimentary straight chain and branched aliphatic alcohol and their unsaturated counterpart.The example of suitable oxygenatedchemicals includes, but are not limited to: methyl alcohol, ethanol, n-propyl alcohol, Virahol, C ₄～C ₂₀Alcohol, methyl ethyl ether, dimethyl ether, Anaesthetie Ether, Di Iso Propyl Ether, formaldehyde, methylcarbonate, dimethyl ketone, acetate, and composition thereof.Representational oxygenatedchemicals comprises lower straight or branched aliphatic alcohol, their unsaturated counterpart.Similar with these oxygenatedchemicalss, can use sulfur-bearing or halid compound.The example of suitable combination thing comprises thiomethyl alcohol, dimethyl thioether, sulfur alcohol, diethyl thioether, monochlorethane, monochloro methane, methylene dichloride, positive alkylogen, has the positive alkyl sulfide of the positive alkyl that comprises about 1～about 10 carbon atoms, and composition thereof.Preferred oxygenatedchemicals is methyl alcohol, dme or its mixture.Most preferred oxygenatedchemicals is a methyl alcohol.

About first reactor effluent, " light olefin " refers to ethene and propylene, and " heavy hydrocarbon fraction " is defined as the fraction that contains the big hydrocarbon of molecular weight ratio propane herein, and it refers to has 4 or more a plurality of carbon atom and note is made C ₄ ⁺Hydrocarbon.It is desirable in first reactor, to have 100% oxygenate rate.This transformation efficiency is regulated by the optimization of catalyst regeneration.Usually in effluent and do not consider thinner or unconverted oxygenatedchemicals, it is as follows to form (amounting to 100%) based on the weight % of carbon:

Alkene is 80～98,

Paraffinic hydrocarbons (comprising methane) is 2～20,

Diolefine is 0.1～0.5,

Aromatic hydrocarbons is less than 0.5.

Among the described alkene, in 100%, light olefin is 60～95%, and the alkene with 4 or more a plurality of carbon atoms correspondingly is 5～40%.Among light olefin, the weight ratio of propylene/ethylene is higher than 1.1 and also advantageously is about 1.1～1.3.

Have among the alkene of 4 or more a plurality of carbon atoms, the butylene of 65～85 weight % is being arranged.The hydrocarbon with 4 or more a plurality of carbon atoms that surpasses 85 weight % and advantageously surpass 95 weight % is C ₄～C ₈Alkene.

About the OCP technology in second reactor, described technology itself is known.In EP1036133, EP 1035915, EP 1036134, EP 1036135, EP 1036136, EP 1036138, EP 1036137, EP 1036139, EP 1194502, EP 1190015, EP 1194500 and EP 1363983, it is described, its content is introduced among the present invention.

The heavy hydrocarbon fraction that produces in first reactor (MTO) (is also referred to as " cracking of olefins reactor " or OCP) conversion herein, to produce the ethene and the propylene of additional quantity in second reactor.Advantageously, find that the catalyzer that produces this conversion comprises the crystalline silicon hydrochlorate that MFI is or MEL is, the crystalline silicon hydrochlorate of described MFI system can be zeolite in this MFI system, silicon zeolite (silicalite) or other silicate arbitrarily, and the crystalline silicon hydrochlorate of described MEL system can be zeolite or other silicate arbitrarily in this MEL system.The example of MFI silicate is ZSM-5 and silicon zeolite.The example of MEL zeolite is ZSM-11 as known in the art.Other example be the described Boralite D of International Zeolite Association and silicon zeolite-2 (Atlas of Zeolite Structure Types, 1987, Butterworths).Preferred crystalline silicon hydrochlorate has hole or passage and the high silicon/al atomic ratio that is limited by ten oxygen rings.

The crystalline silicon hydrochlorate is based on each other by sharing the XO that oxonium ion connects ₄The microporous crystalline inorganic polymer of tetrahedron skeleton, wherein X can be tervalent (for example Al, B ...) or quaternary (for example Ge, Si ...).The crystalline structure of crystalline silicon hydrochlorate is limited by such particular order: the network of tetrahedron element is linked in sequence together with this.The size of crystalline silicon hydrochlorate perforate is perhaps determined by the cationic character that forms the required oxygen atomicity in hole and be present in the hole by the number decision of tetrahedron element.They have the unique combination of following character: but high interior surface area, the even hole ion exchangeable with one or more discrete size, good thermostability and be adsorbed with the ability of organic compounds.Because the hole of these crystalline silicon hydrochlorates is similar dimensionally with many organic molecules of practical study, so their control entering and going out of reactant and product, thereby cause the special selectivity in the catalyzed reaction.Crystalline silicon hydrochlorate with MFI structure has the bidirectional crossed pore system of following bore dia: be 0.53～0.56nm and be 0.51～0.55nm along the sinusoidal passage of [100] along the straight channel of [010].Crystalline silicon hydrochlorate with MEL structure has so bidirectional crossed straight hole system: the aperture that has 0.53～0.54nm along the straight channel of [100].

The crystalline silicon phosphate catalyst has textural property and chemical property, and adopts under the special reaction condition, thereby carries out C easily ₄ ⁺The catalytic cracking of alkene.Different reaction paths can take place on catalyzer.Under processing condition, temperature in is about 400 ℃～600 ℃, is preferably 520 ℃～600 ℃, also more preferably 540 ℃～580 ℃, and the dividing potential drop of alkene is 0.1～2 crust, is most preferably barometric point.The olefin catalytic cracking can be regarded as and comprises via the process of bond rupture generation than short molecule.When having so high silicon/aluminum ratio in the described crystalline silicon phosphate catalyst, can realize stable conversion of olefines, and based on the high propylene yield of alkene.

The MFI catalyzer with high silicon/al atomic ratio that is used for the present invention's second reactor can be by removing aluminium manufacturing from commercially available crystalline silicon hydrochlorate.Typical commercially available silicon zeolite has silicon/al atomic ratio of about 120.Commercially available MFI crystalline silicon hydrochlorate can pass through the steam method modification, and described steam method makes the tetrahedral aluminium in the crystalline silicon hydrochlorate skeleton reduce and the aluminium atom is converted into the octahedra aluminium of amorphous alumina form.Though in steaming step the aluminium atom is removed to form alumina particle with chemical mode from crystalline silicon hydrochlorate skeleton structure, these particles cause the part of skeleton mesopore or passage to be stopped up.This has suppressed cracking of olefins process of the present invention.Therefore, after steaming step, make described crystalline silicon hydrochlorate experience extract (extraction) step, wherein from the hole, remove unbodied aluminum oxide and recover micro pore volume at least in part.By lixiviate (leaching) the step overall dealuminzation effect that physics is removed amorphous alumina generation MFI crystalline silicon hydrochlorate from the hole by forming the water-soluble aluminum complex compound.Like this, will be removed from described hole by its aluminum oxide that forms then by removing aluminium from MFI crystalline silicon hydrochlorate skeleton, described method purpose is to spread all over the uniform basically dealuminzation of whole hole surface realization of catalyzer.This reduces the acidity of catalyzer, thereby has reduced the generation of hydrogen transfer reactions in the cracking process.It is desirable to, acid reduction spreads all over the hole that limits in the crystalline silicon hydrochlorate skeleton basically equably and takes place.This is that hydrocarbon materials can be deep in the described hole because in the cracking of olefins process.Therefore, spread all over whole pore structure in the skeleton and pursue that tart reduces and the minimizing of the hydrogen transfer reactions that made MFI catalyst stability thus reduces.Framework silicon/aluminum ratio can be increased at least about 180 by this method, preferred about 180～1000, more preferably at least 200, more preferably at least 300 and most preferably from about 480 value also.

MEL or MFI crystalline silicon phosphate catalyst can be mixed with tackiness agent (preferred inorganic adhesive), and be configured as the shape of expectation, for example extrude particle.To described tackiness agent select so that its in the catalyzer manufacturing process and the temperature that adopts in the follow-up olefin catalytic cracking process and other condition have tolerance.Described tackiness agent is to be selected from following inorganic materials: clay, silicon oxide, metal oxide (ZrO for example ₂) and/or metal or comprise silicon oxide and the gel of the mixture of metal oxide.Although can use some compound (AlPO for example ₄) aluminium of form, (the AlPO for example because described some compound ₄) be unusual inert and be not tart in essence, however the preferred oxygen-free aluminium of described tackiness agent.If the tackiness agent self that uses with the crystalline silicon hydrochlorate is a catalytic activity, then this may change conversion and/or selectivity of catalyst.The inert material that is used for tackiness agent can suitably play the amount that the work of thinner transforms in order to control, and making can be economical and obtain product in an orderly manner and need not to adopt other to be used to control the means of speed of reaction.It is desirable to provide catalyzer with good shatter strength.This is because in commercial applications, wishes to avoid the Powdered material of catalyst breakage.Usually just adopt such clay or oxide adhesive for the purpose of the shatter strength of improving catalyzer.The particularly preferred tackiness agent that is used for catalyzer of the present invention comprises silicon oxide or AlPO ₄

The relative proportion of the inorganic oxide matrix of particulate crystalline silicon silicate material and tackiness agent can change widely.Usually, based on the weight of composite catalyst, the content of described tackiness agent is 5～95 weight %, more typically is 20～50 weight %.This mixture of crystalline silicon hydrochlorate and inorganic oxide adhesive is called prescription type crystalline silicon hydrochlorate.

When described catalyzer was mixed with tackiness agent, described catalyzer can be mixed with particle, ball, extruded to be other shape perhaps to be configured as spray-dired powder.In the catalytic cracking process of described second reactor, select processing condition to distribute with stable olefin product in highly selective that expectation is provided, the stable conversion of olefines of passing in time and the effluent to propylene or ethene.Use sour density (being high Si/Al atomic ratio) low in the catalyzer and low pressure, high temperature in and help these purposes short duration of contact, all these parameters are to be mutually related and whole storage effect is provided.Select the hydrogen transfer reactions of processing condition to suppress to cause paraffinic hydrocarbons, aromatic hydrocarbons and coke precursors to form.Therefore, process conditions adopts high space velocity, low pressure and high temperature of reaction.LHSV is 5～30h ^-1, be preferably 10～30h ^-1Olefin partial pressures is 0.1～2 crust, is preferably 0.5～1.5 crust (this paper is meant absolute pressure).Particularly preferred olefin partial pressures is normal atmosphere (i.e. 1 crust).Heavy hydrocarbon fraction raw material preferably is being enough to that described raw material is carried charging under the main entrance pressure that passes reactor.Described raw material can be in not diluted or charging under rare gas element (for example nitrogen or steam) dilution situation.Preferably, total absolute pressure is 0.5～10 crust in second reactor.Use low olefin partial pressures (for example normal atmosphere) to trend towards reducing the incidence of hydrogen transfer reactions in the cracking process, it can reduce the possibility that the coke that trends towards catalyst stability is reduced forms again.The cracking of alkene preferably 400 ℃～650 ℃, more preferably 450 ℃～600 ℃, also more preferably 540 ℃～590 ℃, usually carry out under about 560 ℃～585 ℃ feed(raw material)inlet temperature.

For the amount maximization that makes ethene and propylene and the generation of methane, aromatic hydrocarbons and coke is minimized, wish to make that the existence of diolefine minimizes in the raw material.Diolefine to the conversion of monoolefine type hydrocarbon can utilize conventional process for selective hydrogenation for example in the U.S. Patent No. 4,695,560 disclosed method finish, this United States Patent (USP) is incorporated herein by reference.

Described second reactor can be fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor.Typical fluidized-bed reactor is the FCC type fluidized-bed reactor that is used for fluid catalystic cracking in the refinery.Typical moving-burden bed reactor is the continuous catalytic reforming type.As mentioned above, described method can use a pair of parallel connection " (swing) by turns " reactor to carry out continuously.The cracking process of heavy hydrocarbon fraction absorbs heat, and therefore, described reactor should be fit to supply as required heat to keep suitable reaction temperature.Online or the periodic regeneration of catalyzer can be provided by any suitable method as known in the art.

The various preferred catalysts of having found described second reactor demonstrate high stability, particularly can continuous several days (for example being up to 10 days) obtain stable propylene yield.This makes described cracking of olefins process " to rotate " in the reactor two parallel connections to carry out continuously that wherein when a reactor operation, another reactor is carrying out catalyst regeneration.The described catalyzer several times of can regenerating.

Described second reactor effluent comprises methane, light olefin and has the hydrocarbon of 4 or more a plurality of carbon atoms.Advantageously, described second reactor effluent is delivered to fractionator and reclaimed light olefin.Advantageously, the hydrocarbon that will have 4 or more a plurality of carbon atoms is recycled to the ingress of described second reactor under the heavy hydrocarbon blended situation that randomly reclaims with effluent from described first reactor.Advantageously, described hydrocarbon with 4 or more a plurality of carbon atoms is recycled to before the inlet of described second reactor, described hydrocarbon with 4 or more a plurality of carbon atoms is delivered to the after-fractionating device to remove heavy component.In preferred embodiment, the light olefin that light olefin that will reclaim from the effluent of described first reactor and the fractionator after described second reactor reclaim is handled shared recovery zone.

Randomly, in order to regulate the ratio of middle propylene of whole complex body (complex) and ethene, ethene can be recycled to whole or in part second reactor and advantageously be converted into more propylene.This ethene can be from the fractionation section of first reactor or from second reactor.

Randomly, the ethene from first or second reactor can be recycled to first reactor whole or in part, and itself and methyl alcohol merge to form more propylene in first reactor.These operating method are allowed with identical equipment and catalyzer and are responded the market requirement of propylene with respect to the ratio of ethene.

About another embodiment of the present invention, described embodiment relates to by containing oxygen, halide or sulfur-bearing organic raw material makes the method for light olefin, comprising:

Described oxygen, halide or the sulfur-bearing organic raw material of containing contacted first reactor effluent that comprises light olefin and heavy hydrocarbon fraction to form with the catalyzer that is made by metal tripolyphosphate aluminium (MeAPO) molecular sieve under the condition of at least a portion that transforms described raw material effectively in first reactor;

Described light olefin is separated with described heavy hydrocarbon fraction;

Described heavy hydrocarbon fraction under being converted into the condition of light olefin, at least a portion that makes described heavy hydrocarbon fraction is effectively contacted in second reactor;

Wherein said MeAPO is prepared by a method comprising the following steps:

A) formation contains structure influence agent (TIA), organic formwork agent (TEMP), at least a reactive inorganic MeO that is insoluble to TIA basically ₂Source, reactive Al ₂O ₃Source and reactive P ₂O ₅The reaction mixture in source,

B) make the above reaction mixture crystallization of formation thus until the crystal that forms metal tripolyphosphate aluminium;

C) reclaim solid reaction product;

D) it is washed with water with remove described TIA and

E) it is calcined to remove described organic formwork.

In common embodiment, described reaction mixture has the composition that shows with the oxide molar ratiometer:

TEMP/Al ₂O ₃=0.3～5, better is 0.5～2,

MeO ₂/ Al ₂O ₃=0.005～2.0, better is 0.022～0.8,

P ₂O ₅/ Al ₂O ₃=0.5～2, better is 0.8～1.2,

TIA/Al ₂O ₃=3～30, better is 6～20.

In favourable embodiment, TEMP/Al ₂O ₃=0.5～2; MeO ₂/ Al ₂O ₃=0.022～0.8; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

In first preferred implementation, TEMP/Al ₂O ₃=0.5～2; MeO ₂/ Al ₂O ₃=0.022～0.7; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

In second preferred implementation, TEMP/Al ₂O ₃=0.7～2; MeO ₂/ Al ₂O ₃=0.05～0.7; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

In the 3rd preferred implementation, TEMP/Al ₂O ₃=0.7～2; MeO ₂/ Al ₂O ₃=0.05～0.6; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

Metal tripolyphosphate aluminium (MeAPO) molecular sieve that uses above method to make has the layered crystal form.

In common embodiment, metal tripolyphosphate aluminium (MeAPO) molecular sieve that uses above method to make has the layered crystal form, and it has by formula H after synthetic and calcining _xMe _yAl _zP _kO ₂The experience chemical constitution on anhydrous basis of expression, wherein,

y+z+k＝1

x≤y

Y have 0.0008～0.4 and better be 0.005～0.18 value,

Z have 0.25～0.67 and better be 0.38～0.55 value,

K have 0.2～0.67 and better be 0.36～0.54 value,

Described molecular sieve mainly has the platelet form.

Y, z in this common embodiment and k value by each composition described in the above-mentioned common embodiment method than obtaining.

In favourable embodiment, y has 0.005～0.18 value, and z has 0.38～0.55 value and k and has 0.36～0.54 value.

In first preferred implementation, y has 0.005～0.16 value, and z has 0.39～0.55 value, and k has 0.37～0.54 value.

In second preferred implementation, y has 0.011～0.16 value, and z has 0.39～0.55 value, and k has 0.37～0.54 value.

In the 3rd preferred implementation, y has 0.011～0.14 value, and z has 0.40～0.55 value, and k has 0.38～0.54 value.

Y, z in above-mentioned favourable, first, second and the 3rd embodiment and k value are by using in favourable, first, second and the 3rd embodiment of aforesaid method respectively described each composition than obtaining.

In favourable embodiment, the MeAPO that makes by above method has structure C HA or AEI or its mixture basically.Preferably, they have structure SAPO 18 or SAPO34 or its mixture basically.

That below enumerated relevant with synthetic, the details of first reactor MeAPO, the operational condition of described first reactor, the details of second reactor, the operational condition of described second reactor etc. all conditions is applicable to described other embodiment of the present invention.

Fig. 9 has illustrated the specific embodiment of the present invention.The effluent of first reactor is delivered to fractionator 11.Overhead product (C1～C3 cut that comprises light olefin) is delivered to shared recovery zone (not shown) via pipeline 2.Bottom materials (heavy hydrocarbon fraction) is delivered to described second reactor (OCP reactor) via pipeline 3.The effluent of described second reactor (OCP reactor) is delivered to fractionator 8 via pipeline 10.Overhead product (C1～C3 cut that comprises light olefin) is delivered to shared recovery zone (not shown) via pipeline 9.Bottom materials (hydrocarbon with 4 or more a plurality of carbon atoms) is delivered to fractionator 5.Overhead product (have 4 to the hydrocarbon of 5 carbon atoms) basically is recycled to the inlet of described second reactor via pipeline 4.Bottom materials (hydrocarbon that has 6 or more a plurality of carbon atoms basically) is removed via pipeline 6.

Can comprise the additional step that contains the oxygen raw material from the hydrocarbon manufacturing of for example oil, coal, Tar sands, shale, biomass and Sweet natural gas from the method that contains oxygen raw material manufacturing olefin product.The method that manufacturing contains the oxygen raw material is as known in the art.These methods comprise: fermenting is alcohol or ether; Make synthetic gas, then described synthetic gas is converted into alcohol or ether.Synthetic gas can followingly be made: under the situation of gas raw material, by the currently known methods manufacturing of for example steam reformation, self-heating recapitalization and partial oxidation; Perhaps under the situation of solid (coal, organic waste) or liquid starting material, by using oxygen and steam to reform or gasifying manufacturing.Can be by methane carried out oxidation making methyl alcohol, methyl sulphur and methyl halide by means of containing dioxy, sulphur or halogenide in oxygen, halide or the organic compounds containing sulfur accordingly.

Those skilled in the art it will also be appreciated that to make and utilize olefin product polymerization that molecular sieve of the present invention makes by oxygenatedchemicals to conversion of olefines reaction with formation polyolefine, especially polyethylene and polypropylene.

Embodiment

In following examples:

EG refers to ethylene glycol,

Eth refers to ethanol,

MeOH nail alcohol,

XRD refers to X-ray diffraction,

SEM refers to scanning electron microscopy,

Aerosil

It is the fumed silica that provides by Degussa.

Embodiment 1～3

The reaction mixture that in polytetrafluoroethylcontainer container, prepares TIA, phosphoric acid (in water, concentration 85%) and TEAOH solution (in water, concentration 40%).The Al source and the Si source that in this solution, add respective amount respectively.This slurry at room temperature mixes about 30 minutes until evenly.Then, described polytetrafluoroethylcontainer container is put into stainless steel autoclave.This autoclave remains under the temperature.After being cooled to room temperature, take out sample, washing is also dry.Solid after synthetic carried out with separating by centrifugal of liquid phase.Isolated solid was calcined 10 hours in airflow 110 ℃ of following dried overnight and under 600 ℃.Ratio and operational condition are in following table.This process is applied to all embodiment.

Embodiment 1～3

Embodiment	??3
		Mole is formed	??1TEAOH/0.1?SiO 2/0.9?P 2O 5/0.9?Al 2O 3/12TIA
TEAOH (in water, concentration 40%), g	??28.03
		Virahol Al 98%, g	??27.82
??TIA，g	??27.81MeOH
		??Aerosil?200，g	??0.50
??H 3PO 4(in water, concentration 85%), g	??15.80
		Condition	160 ℃, 3 days
??XRD	??SAPO-18

??SEM

Stratiform

Embodiment 4～6

Embodiment	??4
		Mole is formed	??1TEAOH/0.3?SiO 2/1?P 2O 5/1?Al 2O 3/12TIA
TEAOH (in water, concentration 35%), g	??28.00
		Virahol Al 98%, g	??27.80
??TIA，g	??50.15EG
		??Aerosil?200，g	??1.34
??H 3PO 4(in water, concentration 85%), g	??15.30
		Condition	3 days, 160 ℃
??XRD	??SAPO-18
		??SEM	Stratiform

Embodiment 7～8

Embodiment	??7
		Mole is formed	??1TEAOH/0.6?SiO 2/1?P 2O 5/1?Al 2O 3/12TIA
TEAOH (in water, concentration 35%), g	??28.10
		Virahol Al 98%, g	??27.80
??TIA，g	??50.08EG
		??Aerosil?200，g	??2.50
??H 3PO 4(in water, concentration 85%), g	??15.30
		Condition	3 days, 160 ℃

??XRD	??SAPO-18
		??SEM	Stratiform

Embodiment	??8
		Mole is formed	??1TEAOH/0.6?SiO 2/0.9?P 2O 5/0.9?Al 2O 3/12TIA
TEAOH (in water, concentration 40%), g	??28.03
		Virahol Al 98%, g	??27.82
??TIA，g	??39.99Eth
		??Aerosil?200，g	??3.06
??H 3PO 4(in water, concentration 85%), g	??15.80
		Condition	3 days, 160 ℃
??XRD	??SAPO-34
		??SEM	Stratiform, Fig. 2

Embodiment 9

Synthetic under comparatively high temps

Embodiment	??9
		Mole is formed	??1TEAOH/0.3?SiO 2/1?P 2O 5/1?Al 2O 3/12TIA
TEAOH (in water, concentration 35%), g	??28.10
		Virahol Al 98%, g	??27.80
??TIA，g	??50.08EG
		??Aerosil?200，g	??1.34
??H 3PO 4(in water, concentration 85%), g	??15.50
		Condition	3 days, 190 ℃
??XRD	??SAPO-18
		??SEM	Stratiform

Embodiment 10～11

The TIA of reduction amount

Embodiment 12

Template with the reduction amount is synthetic

Embodiment	??12
		The mole of gel is formed	??0.7TEAOH/0.1?SiO 2/1?Al 2O 3/15?EG/1P 2O 5
TEAOH (in water, concentration 35%), g	??9.81
		Virahol Al 98%, g	??13.89
??TIA，g	??31.35EG
		??Aerosil?200，g	??0.20
??H 3PO 4(in water, concentration 85%), g	??7.69
		Condition	160 ℃, 4 days
??XRD	??SAPO-18
		??SEM	Stratiform

Embodiment 13

Template with the raising amount in the presence of EG is synthetic

Embodiment	??13
		Mole is formed	??2TEAOH/0.1?SiO 2/1?Al 2O 3/1?P 2O 5/6EG
TEAOH (in water, concentration 35%), g	??28.00
		Virahol Al 98%, g	??13.90
??TIA，g	??12.54EG
		??Aerosil?200，g	??0.20
??H 3PO 4(in water, concentration 85%), g	??7.69
		Condition	160 ℃, 4 days
??XRD	??SAPO-18
		??SEM	Stratiform, Fig. 3

Embodiment 14

Synthetic under low Si content

Embodiment	??14
		Mole is formed	??1TEAOH/0.05?SiO 2/1?Al 2O 3/1?P 2O 5/12EG

TEAOH (in water, concentration 35%), g	??14.00
		Virahol Al 98%, g	??13.90
??TIA，g	??25.08EG
		??Aerosil?200，g	??0.10
??H 3PO 4(in water, concentration 85%), g	??7.7
		Condition	160 ℃, 4 days
??XRD	??SAPO-18
		??SEM	Stratiform

Comparative Examples I

The main points of this prescription: The Si source must dissolve in the alcoholNot all in the present invention Si source all dissolves among the TIA.

According to the scheme of US 6540970, in the presence of alcohol, use the synthetic SAPO in organic Si source:

Embodiment	Comparative Examples I
		Prescription	??US?6?540?970?B1
Mole is formed	??2TEAOH/0.1?SiO 2/1?Al 2O 3/1?P 2O 5/50?H 2O/8Eth
		?H 2O，g	??19.90
TEAOH (in water, concentration 35%), g	??60.00
		Al source (catapal B), it is hydrated aluminum oxide for g	??10.04
Ethanol, g	??26.28
		Si source TEOS, g	??1.52
?H 3PO 4(in water, concentration 85%), g	??16.44
		Condition	195 ℃, 1 day
?XRD	??SAPO-34/18
		?SEM	Cubic system, Fig. 4

Form according to this prescription synthetic sample is different with stratiform.In fact, the very special spherical morphology of SAPO-34 sample has been described in this patent.Crystallite has the width of about 0.5 μ m～about 30 μ m at the size place of their maximums.

The reproduction of the synthetic embodiment of SAPO-18 has produced the material with cubic system.

Comparative Example II

Synthetic (the old prescription) of SAPO-18

-Verified Syntheses of Zeolitic Materials, H.Robson, Elsevier, the 81st page,

-Catalysis?Letters?28(1994)241-248

-J.Chem.Soc.，Chem.Comm.，1994，603-604

-J.Phys.Chem.1994，98，10216-10224

Embodiment	Comparative Example II
		Mole is formed	??0.4SiO 2∶1Al 2O 3∶0.9P 2O 5∶50H 2O∶1.9DPEA
??H 2O，g	??66.92
		??H 3PO 4(in water, concentration 85%), g	??16.73
Al source (catapal B), it is hydrated aluminum oxide for g	??11.35
		??Aerosil?200，g	??1.96
??DPEA，g	??20.00
		Condition	160 ℃, 7 days
??XRD	??SAPO-18
		??SEM	Cube, Fig. 5

Comparative Example II I

Synthesize SAPO according to the prescription of US 6 334 994, under high and low Si content

Embodiment	Comparative Example II Ia	Comparative Example II Ib
			The prescription reference	??US?6?334?994	??Microporous?Mesoporous??1999，29，159
Mole is formed	??0.075SiO 2/Al 2O 3/0.98??P 2O 5/2TEAOH	??0.3SiO 2/Al 2O 3/0.98P 2O 5??/2TEAOH
			?H 2O，g	??18.06	??36.08
Virahol Al 98%, g	??13.80	??27.23
			?H 3PO 4(in water, concentration 85%), g	??7.52	??15.17
?HCl，g	??0.12	??0.20
			Ludox AS 40 (40% silicon oxide), g	??0.54	??4.00
TEAOH (in water, concentration 35%), g	??28.20	??56.08
			?XRD	??SAPO-18	??SAPO-34
?SEM	Stratiform cube, Fig. 6	Cube, Fig. 7

Comparative Examples I V (US 6 953 767 B2)

Contriver among the US 6953767B2 has described the synthetic of SAPO phase mixed structure.Regulate 18/34 phase ratio by the slewing rate that changes autoclave between synthesis phase.

The result shows that phase composite is reproducible, but form is not lamellated.

Embodiment	Comparative Examples I V is identical with the embodiment 1 of US 6 953 767 B2
		Mole is formed	??0.15SiO 2/1Al 2O 3/1P 2O 5/1TEAOH/35H 2O
Condition	175 ℃, 8 hours
		Rotating speed, rpm	??60
??H 2O，g	??32.13
		Aluminum oxide (Condea Pural SB), g	??19.85
??H 3PO 4(in water, concentration 85%), g	??33.55
		Ludox AS 40 (40% silicon oxide), g	??3.32
TEAOH (in water, concentration 35%), g	??61.40
		Gross weight, g	??150.25
??XRD	??AEI/CHA～0.2
		??SEM	Stratiform cube, Fig. 8

Embodiment 15

In fixed bed, downflow system stainless steel reactor, cling to the pressure and the WHSV=1.6h of gauge pressure at 450 ℃, 0.5 ^-1On the 2g catalyst sample, carry out catalyst test down with pure methanol feedstock.Catalyst fines is pressed into thin slice and crushes is 35～45 purpose particles.Before carrying out catalysis operation with all catalyzer at mobile N ₂Be heated to temperature of reaction (5Nl/h).The analysis of product is undertaken by the gas-chromatography that is equipped with capillary column is online.Methanol conversion 100% and just in effluent DME has appearred and before maximum catalyst activity under the catalytic performance of MeAPO molecular sieve relatively.

Make and contain non-cyclic olefin C basically ₄ ⁺The raw material of (heavy hydrocarbon fraction) in the presence of alumina silicate catalyst, in fixed-bed reactor at 575 ℃, LHSV=10h ^-1, experience catalytic cracking (second reactor) under the P=1.5 crust absolute pressure.Thereby comprising the dealumination treatment that experiences decatize and acid treatment combination, this catalyzer provides the commercially available silicon zeolite of about 250 Si/Al ratio.The detailed process of Preparation of Catalyst has been described in EP1194502B1 cited above.

Used and adopted the mathematical model of the conversion factor of deriving to simulate the OCP performance by many tests of different material.Form and required removing based on the logistics of going to the OCP reactor, the best logistics of C4 and heavy component is recycled to the OCP reactor." OCP charging non-cyclic olefin C ₄ ⁺" below several row shown the heavy hydrocarbon flow rate (flow rate) that is delivered to OCP (second reactor).Several row of " MTO+OCP " below show ethene that combination produced and the propylene by first reactor (MTO) and second reactor (OCP).

The result is in following table 1.Value in the table 1 is the weight percent based on carbon.

Embodiment 16

In fixed bed, downflow system stainless steel reactor, cling to the pressure and the WHSV=2.9h of gauge pressure at 450 ℃, 0.2 ^-1Under use methyl alcohol/H ₂Catalyst test is carried out in the charging of O:70/30 on the 2g catalyst sample.Catalyst fines is pressed into thin slice and crushes is 35～45 purpose particles.Before carrying out catalysis operation with all catalyzer at mobile N ₂Be heated to temperature of reaction (5Nl/h).The analysis of product is undertaken by the gas-chromatography that is equipped with capillary column is online.Methanol conversion 100% and just in effluent DME has appearred and before maximum catalyst activity under the catalytic performance of SAPO molecular sieve relatively.

Make the raw material that contains C4 and C5 alkene (heavy hydrocarbon fraction) in the presence of alumina silicate catalyst, in the fixed bed pilot plant at 575 ℃, LHSV=10h ^-1, experience catalytic cracking (second reactor) under the P=1.5 crust absolute pressure.Thereby comprising the dealumination treatment that experiences decatize and acid treatment combination, this catalyzer provides the commercially available silicon zeolite of about 250 Si/Al ratio.The detailed process of Preparation of Catalyst has been described in EP1194502B1 cited above.

Used and adopted the mathematical model of the conversion factor of deriving to simulate the OCP performance by many tests of different material.Based on vapor composition of going to the OCP reactor and required removing, the best logistics of C4 and heavy component is recycled to the OCP reactor.Several row of " OCP charging non-cyclic olefin C4+ " below have shown the heavy hydrocarbon flow rate that is delivered to OCP (second reactor).Several row of " MTO+OCP " below show ethene that combination produced and the propylene by first reactor (MTO) and second reactor (OCP).

The result is in following table 2.Value in the table 2 is the weight percent based on carbon.

Table 2

	??SAPO-18	??SAPO-34
Form	Thin layer	Stratiform cube
				Embodiment 12	Comparative Example II Ia
Methane in the MTO effluent	??2.0	??2.5
			C2 purity	??100	??100
C3 purity	??100	??98
			??C3/C2	??1.2	??1.0
??C2+C3	??78.0	??80.0
			Ethene in the MTO effluent	??36.0	??41.0
Propylene in the MTO effluent	??42.0	??39.0

The OCP charging is from the non-cyclic olefin C4～C5 of MTO effluent
			C4 alkene	??15.0	??12.5
C5 alkene	??4.0	??3.0
			Be delivered to the alkene summation of OCP	??19.0	??15.5
?MTO+OCP
			Ethene	??38.8	??43.3
Propylene	??53.1	??48.1
			?C3/C2	??1.4	??1.1
?C2+C3	??91.9	??91.4

Claims (39)

1. make the method for light olefin by containing oxygen, halide or sulfur-bearing organic raw material, comprising:

Described oxygen, halide or the sulfur-bearing organic raw material of containing contacted first reactor effluent that comprises light olefin and heavy hydrocarbon fraction to form with the catalyzer that is made by metal tripolyphosphate aluminium (MeAPO) molecular sieve with layered crystal form under the condition of at least a portion that transforms described raw material effectively in first reactor;

Described light olefin is separated with described heavy hydrocarbon fraction;

Described heavy hydrocarbon fraction under being converted into the condition of light olefin, at least a portion that makes described heavy hydrocarbon fraction is effectively contacted in second reactor;

Wherein said MeAPO has by formula H after synthetic and calcining _xMe _yAl _zP _kO ₂The experience chemical constitution on anhydrous basis of expression, wherein

y+z+k＝1，

x≤y，

Y has 0.0008～0.4 value,

Z has 0.25～0.67 value,

K has 0.2～0.67 value,

Described molecular sieve mainly has the platelet form, and wherein width (W) and thickness (T) satisfy:

W/T≥10。

2. the process of claim 1 wherein that y has 0.005～0.18 value.

3. each method in the aforementioned claim, wherein z has 0.38～0.55 value.

4. each method in the aforementioned claim, wherein k has 0.36～0.54 value.

5. each method in the aforementioned claim, wherein y has 0.005～0.18 value, and z has 0.38～0.55 value, and k has 0.36～0.54 value.

6. the method for claim 5, wherein y has 0.005～0.16 value, and z has 0.39～0.55 value, and k has 0.37～0.54 value.

7. the method for claim 6, wherein y has 0.011～0.16 value, and z has 0.39～0.55 value, and k has 0.37～0.54 value.

8. the method for claim 7, wherein y has 0.011～0.14 value, and z has 0.40～0.55 value, and k has 0.38～0.54 value.

9. each method in the aforementioned claim, wherein Me is a silicon.

10. each method in the aforementioned claim, wherein T≤0.15 μ m.

11. the method for claim 10, wherein T≤0.10 μ m.

12. the method for claim 11, wherein T≤0.08 μ m.

13. the method for claim 12, wherein T is 0.01～0.07 μ m.

14. the method for claim 13, wherein T is 0.01～0.04 μ m.

15. each method in the aforementioned claim, wherein W/T is 10～100.

16. each method in the aforementioned claim, wherein said structure are essentially CHA or AEI or its mixture.

17. each method in the aforementioned claim, wherein said structure are essentially SAPO 18 or SAPO 34 or its mixture.

18. make the method for light olefin by containing oxygen, halide or sulfur-bearing organic raw material, comprising:

Described oxygen, halide or the sulfur-bearing organic raw material of containing contacted first reactor effluent that comprises light olefin and heavy hydrocarbon fraction to form with the catalyzer that is made by metal tripolyphosphate aluminium (MeAPO) molecular sieve under the condition of at least a portion that transforms described raw material effectively in first reactor;

Described light olefin is separated with described heavy hydrocarbon fraction;

Described heavy hydrocarbon fraction under being converted into the condition of light olefin, at least a portion that makes described heavy hydrocarbon fraction is effectively contacted in second reactor;

Wherein said MeAPO is prepared by a method comprising the following steps:

A) formation contains structure influence agent (TIA), organic formwork agent (TEMP), at least a reactive inorganic MeO that is insoluble to TIA basically ₂Source, reactive Al ₂O ₃Source and reactive P ₂O ₅The reaction mixture in source,

B) make the above reaction mixture crystallization of formation thus until the crystal that forms metal tripolyphosphate aluminium;

C) reclaim solid reaction product;

D) it is washed with water with remove described TIA and

E) it is calcined to remove described organic formwork.

19. the method for claim 18, wherein said reaction mixture have the composition that shows with following oxide molar ratiometer:

TEMP/Al ₂O ₃＝0.3～5，

MeO ₂/Al ₂O ₃＝0.005～2.0，

P ₂O ₅/Al ₂O ₃＝0.5～2，

TIA/Al ₂O ₃＝3～30。

20. each method in the claim 18～19, wherein said ratio TEMP/Al ₂O ₃=0.5～2.

21. each method in the claim 18～20, wherein said ratio MeO ₂/ Al ₂O ₃=0.022～0.8.

22. each method in the claim 18～21, wherein said ratio P ₂O ₅/ Al ₂O ₃=0.8～1.2.

23. each method in the claim 18～22, wherein said ratio TIA/Al ₂O ₃=6～20.

24. the method for claim 18, wherein TEMP/Al2O3=0.5～2; MeO ₂/ Al ₂O ₃=0.022～0.8; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

25. the method for claim 24, wherein TEMP/Al ₂O ₃=0.5～2; MeO ₂/ Al ₂O ₃=0.022～0.7; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

26. the method for claim 25, wherein TEMP/Al ₂O ₃=0.7～2; MeO ₂/ Al ₂O ₃=0.05～0.7; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

27. the method for claim 26, wherein TEMP/Al ₂O ₃=0.7～2; MeO ₂/ Al ₂O ₃=0.05～0.6; P ₂O ₅/ Al ₂O ₃=0.8～1.2 and TIA/Al ₂O ₃=6～20.

28. each method in the claim 18～27, wherein Me is a silicon.

29. each method in the claim 18～28, wherein said structure influence agent (TIA) is selected from 1,2-propylene glycol, 1, ammediol, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, glycerine or ethylene glycol.

30. each method in the claim 18～29, wherein said structure are essentially CHA or AEI or its mixture.

31. each method in the claim 18～30, wherein said structure are essentially SAPO 18 or SAPO 34 or its mixture.

32. each method in the aforementioned claim, wherein said to contain oxygen (containing aerobic) compound be methyl alcohol, dme or its mixture.

33. each method in the aforementioned claim, the catalyzer of wherein said second reactor comprise the crystalline silicon hydrochlorate of MFI system or MEL system.

34. the method for claim 33, wherein said catalyzer are ZSM-5 or silicon zeolite.

35. each method in the aforementioned claim wherein will or be returned the inlet of described first reactor from the effluent of described first reactor from the ethene recirculation whole or in part of the effluent of described second reactor.

36. each method in the aforementioned claim wherein will or be returned the inlet of described second reactor from the effluent of described first reactor from the ethene recirculation whole or in part of the effluent of described second reactor.

37. each method in the aforementioned claim is wherein delivered to the effluent of described second reactor fractionator so that (i) light olefin is separated with the hydrocarbon that (ii) has 4 or more a plurality of carbon atoms;

Described hydrocarbon with 4 or more a plurality of carbon atoms is recycled to the ingress of described second reactor.

38. each method in the aforementioned claim, wherein make ethene randomly with the further polymerization of one or more comonomers.

39. each method in the aforementioned claim, wherein make propylene randomly with the further polymerization of one or more comonomers.

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